O-alkyl-s-alkyl-s-{8 1,2-bis(alkoxyalkoxy, benzyloxy, alkylamino) carbonyl ethyl{9 dithiophosphates

ABSTRACT

R5 and R6 each represents hydrogen, methyl or allyl and are effective against insects and representatives of the order Acarina.   WHENEVER R1 represents methyl or ethyl, R2 represents n-propyl, n-butyl, i-butyl, sec.butyl, n-pentyl, sec.pentyl, or methoxyethyl, R3 and R4 each represents methoxyethoxy, ethoxyethoxy, ethoxyethoxyethoxy, benzyloxy, or the group   New thiolphosphoric acid esters, their manufacture and use as pesticides is disclosed. The compounds corresopond to the formula

United States Patent 1191 Beriger 14 1 Mar. 18, 1975 PHOSPFKTITS [75}Inventor: Ernst Beriger,Allschwil,

Switzerland [73] Assigncc: Ciba-Geigy Corporation, Ardsley.

122 Filed: Apr. 25, 1973 1211 Appl. No.2 354,405

[30] Foreign Application Priority Data Apr. 27, 1972 Switzerland 6265/72[52] U.S. Cl 260/942, 260/943, 424/212 [51] Int. Cl. C07f 9/16, AOln9/36 [58] Field of Search 260/942 [56] References Cited UNITED STATESPATENTS 3,309,371 3/1967 Curry et a1 260/925 FORElGN PATENTS ORAPPLICATIONS 1,001,065 8/1965 Ignited Kingdom 260/942 PrimaryExaminerAnton H. Sutto Attorney, Agent, or FirmFrederick H. Rabin [57]ABSTRACT New thiolphosphoric acid esters, their manufacture and use aspesticides is disclosed. The compounds corresopond to the formula 0 0 RP R S S-CH-COR CH COR whenever R represents methyl or ethyl, Rrepresents n-propyl, n-butyl, i butyl, sec.butyl, n-pentyl, sec.pentyl,or methoxyethyl, R and R each represents methoxyethoxy, ethoxyethoxy,ethoxyethoxyethoxy benzyloxy, or the group R5 I and R and R eachrepresents hydrogen. methyl or allyl ofthe order Acarina.

7 Claims, N0 Drawings 1 O-ALKYL-S-ALKYL-S-{l,2-BIS(ALKOXYALOXY,BENZYLOXY, ALKYLAMINO)CARBONYL LIP I HQSREAW The present inventionrelates to thiophosphoric acid esters, processes for their manufacture,and to their use in pest control.

The thiolphosphoric acid esters have the formula wherein R, representsmethyl or ethyl, R represents n-propyl, n-butyl, i-butyl, sec.butyl,n-pentyl, sec.pentyl, or methoxyethyl, R and R, each representsmezyloxy, or the group and R and R each represent hydrogen, methyl orallyl.

Preferred compounds on account of their activity are those ofthe formulaI, wherein R represents methyl or ethyl, R represents n-propyl, sec.amylor methoxyethyl, and R and R represent benzyloxy, or methoxyethoxy.

thoxyethoxy, ethoxyethoxy, ethoxyethoxyethoxy, ben- Analogous compoundsare described as insecticides In the formulae II to XI, R, to R have themeanings given for the formula I, R represents alkyl with l to 4 carbonatoms, X represents oxygen or sulphur, Hal represents chlorine, bromine,or iodine, and M represents ammonium, alkylammonium with 1 to 4 carbonatoms in the alkyl moiety, or alkali metal.

In reaction 1 it is sometimes necessary to use catalysts, e.g. potassiumiodide, Reaction 2 is initiated by using ultraviolet light, peroxides,e.g. hydrogen peroxide, or hydroquinone. Reactions 1 to 4 are carriedout at a reaction temperature between 0 and 90C, in particular at 20 toC, at normal pressure and in solvents or diluents.

Examples of suitable solvents or diluents are: ethers and etherealcompounds, such as diethyl ether, dipropyl ether, dioxan,t'etrahydrofuran; amides, such as N,N-dialkylated carboxylic amides;aliphatic, aromatic, and halogenated hydrocarbons, in particularbenzene. toluene, xylene, chloroform, chlorobenzene; nitriles. such asaceto nitrile; dimethyl sulphoxide, ketones. such as acetone, methylethyl ketone, water. Ethanol is also suitable for processes 3 and 4.

The starting materials of the formulae II, IV and VI can be manufacturedin analogous manner to known methods, e.g. those described in OrganicReactions II, pages 1 to 48.

The compounds of the formula I have a broad biocidal activity spectrumand can be used for combating diverse kinds of plant and animal pestsThe compounds of the formula I possess in particular insecticidal andacaricidal properties and can be used against all development stages,e.g. eggs, larvae. pupae. nymphs, and adults of insects andrepresentatives of the order Acarina, for example against insects of thefamilies: Tetigonidae, Gryllidae, Gryllotalpidae, Blattidae, Peduviidae,Phyrrohocoriae, Cimicidae, Delphacidae, Aphididae, Diaspididae,Pseudococcidae, Scarabaeidae, Dermestidae, Coccinellidae, Tenebrionidae,Chrysomelidae, Bruchidae, Tineidae, Noctuidae, Lymatriidae, Pyralidae,Culcidae, Tipulidae, Stomoxydae, Trypetidae, Muscidae, Calliphoridae andPulicidae, also Acarida of the families Ixodidae, Argasidae,

or task (VIII) I (no R flal I n o n l r-sn 1) R28 HlIffiHORB cH -coR(III) 4 R1. g P-Sil Gil-COR n s (IV) (V) 3) R 0 s s I r-s-t wcoa R7OC-SH(VII) R 0 cu -COR (1 i -sn 0o Tetranychidae and Dermanyssidae. Theinsecticidal and/or acaricidal action can be substantially broadened andadapted to suit the particular circumstances by the addition of otherinsecticides and/or acaricides.

Suitable additives include, for example, the following activesubstances:

Organic phosphorus compounds Bis-0,0-diethylphosphoric acid anhydride(TEPP) Dimethyl-(2,2,2-trichloro-1-hydroxyethyl)- phosphonate(TRICHLORFON) l,2-dibromo-2,2-dichloroethyldimethylphosphate (NALED)2,2-dichlorovinyldimethylphosphate (DICHLORVOS)2-methoxycarbamyl-l-methylvinyldimethylphosphate (MEVINPHOS) Dimethyll-methyl-2-( methylvinyldimethylphosphate cis (MONOCROTOPHOS)3-(dimethoxyphosphinyloxy)-N,N-dimethyl-ciscrotonamide (DICROTOPHOS)2-chloro-Z-diethylcarbamoyll -methylvinyldimethylphosphate(PHOSPHAMIDON) 0,0-di ethyl-O(or S)-2-(ethylthio)-ethyl thiophosphate(DEMETON) v S-ethylthioethyl-0,0-dimethyl-dithiophosphate (THI- OMETON)0,0-diethyl-S-ethylmercaptomethyldithiophosphate (PHORATE)0,0-diethyl-S-2-(ethylthio)ethyldithiophosphate (DI- SULFOTON0,0-dimethyl-S-2-(ethylsulphinyl)ethylthiophosphate (OXYDEMETON METHYL)0,0-dimethyl-S-( l,2-dicarbethoxyethyldithiophosphate (MALATHION)0,0,0,0-tetraethyl-S,S'-methylene-bisdithiophosphate (ETHION)O-ethyl-S,S-dipropyldithiophosphate 0,0-dimethyl-S-(N-methyl-N-formylcarbamoylmethyl )-dithiophosphate (FOR- MOTHION)0,0-dimethyl-S-(N-methylcarbamoylmethyl)- dithiophosphate (DIMETHOATE)0,0-dimethyl-O-p-nitrophenylthiophosphate (PA- RATHION-METHYL)0,0-diethyl-O-p-nitrophenylthiophosphate (PARA- THION)O-ethyl-O-p-nitrophenylphenylthiophosphate (EPN)0,0-dimethyl-O-(4-nitro-m-tolyl)-thiosphophate (FENlTROTI-llON)0,0-dimethyl-O-2,4,5-trichlorophenylthiophosphate (RONNEL)O-ethyl-O-2,4,5-trichlorophenylethylthiophosphate (TRICHLORONATE)0,0-dimeth'yl-O-2,5-dichloro-4-bromophenylthiophosphate (BROMOPHOS)0,0-dimethyl-O-(2,5-dichloro-4-iodophenyl)- thiophosphate (JODOFENPHOS)4-tert.butyl-2-chlorophenyl-N-methyl-O- methylamidophosphate (CRUFOMATE)0,0-dimethyl-O-(3-methyl-4-methylmercaptophenyl)- thiophosphate(FENTHION) Isopropylamino-O-ethyl-O-(4-methylmercapt0-3-methylphenyl)-phosphate0,0-diethyl-O-p-(methylfulphinyl)phenylthiophosphate (FENSULFOTHION)O-p-(dimethylfulphamido)-phenyl-O,O-dimethylthiophosphate (FAMPHUR)0,0,0 ,0 '-tetramethyl-0,0 -thiodi-p-phenylenethio- RhPSPJELQW a.

4 O-ethyl-S-phenyl-ethyldithiophosphate 0,0-dimethyl-O-(a-methylbenzyl-3-hydroxycrotonyl)- phosphate 2-chlorol2,4-dichlr0phenyl)vinyldiethylphosphate (CHLORFENVINPHOS) l-chlorol2,4,5-trichlor0phenyl )vinyldimethylphosphateO-[Z-chloro-l-(2,5-dichlorophenyl)]vinyl-0,0- 'diethylthiophosphatePhenylglyoxylonitriloxime-0,0-Diethylthiophosphate (PHOXIM)0,0-diethyl-O-( 3-chloro-4-methyl-2-oxo-2-H- lbenzopyran-7-yl)-thiophosphate (COUMAPHOS)2,3-p-dioxandithiol-S,S-bis(0,0-diethyldithiophosphate) (DIOXATHION)5-[(6-chloro-2-oxo-3-benzoxazolinyl)methyl]0,0- diethyldithiophosphate(PHOSALONE) 2-(diethoxyphosphinylimino)-l ,3-dithiolane0,0-dimethyl-S-[2-methoxy-l ,3,4-thiadiazol-5-(4H)- gnylflfl-znstbllldih 0,0-dimethyl-S-phthalimidomethyl-dithi0phosphate (IMIDAN)0,0-diethyl-O-( 3 ,5 ,6-trichlor0-2- pyridyl)thiophsophate0,0-diethyl-O-2-pyrazinylthiophosphate ZIN) 0,0-diethyl-O-(2-isopropyl-4-methyl-6-pyrimidyl )thiophosphate (DIAZINON)0,0-diethyl-O-(2-quinoxalyl)thiophosphate 0,0-dimethyl-S-(4-oxo-l,2,3-benzotriazin-3(4H ylmethyl)-dithiophosphate (AZINPHOSMETHYL)0,0-diethyl'S-(4-0xo-l ,2,3-benzotriazin-3(4H ylmethyl)-dithiophosphate(AZINPHOSETHYL) S-[(4,6-diamino-s-triazin-2-yl)methyl]-0,0-dimethyldithiophosphate (MENAZON)0,0-dimethyl-O-(3-chloro-4-nitrophenyl)thiophosphate (CHLORTHION)0,0-dimethyl-O(or S )-2-( ethylthioethyl )thiophosphate(DEMETON-S-METHYL)2-(0,0-dimethyl-phosphoryl-thiomethyl)-5-methoxypyrone-4-3,4-dichlorobenzyl-triphenylphosphoniumchloride0,0-diethyl-S-(2,5-dichlorophenylthiomethyl)dithiophosphate (PHENKAPTON)0,0-diethyl-O-( 4-methyl-cumarinyl-7 )-thioph0sphate (THlONA- (POTASAN)5-amino-bis(dimethylamino)ph0sphinyl-3-phenyl- 1,2,4-tria2ole(TRIAMIPHOS) N-methyl-5-(0,0-dimethylthiolphosphoryl)-3-thiavaleramide(VAMIDOTHION) 0,0-diethyl-O-[Z-dimethylamino-4-methylpyrimidyl-(6)]-thiophosphate (DIOCTHYL) 0,0-dimethyl-S-(methylcarbamoylmethyl)-thiophosphate (OMETHOATE) O-ethyl-O-( 8-quinolinyl)-phenylthiophosphonate (OXINOTHIOPHOS)O-methyl-S-methyl-amidothiophosphate (MONITOR)O-methyl-O-(2,5-dichloro'-4-bromophenyl)-benzothiophosphate (PHOSVEL)0,0,0,0-tetrapropyldithiophosphate3-(dimeth0xyphosphinyloxy)-N-methyl-N-methoxycis-crotonamide0,0-dimethyl-S-( N-ethylcarbam oylm ethyl )dithiophosphate(ETHOATE-METHYL) 0,0-diethyl-S-( N -isopropylcarbamoylmethyldithiophosphate (PROTHOATE) S-N-( l-cyanol -methylethyl)carbamoylmethyldiethyl- 215 SPhQ FLQYANIHQAIEX 9Z-allyloxyphenyl-N-methyl-carbamate4methoxycarbonylamino-3-isopropylphenyl-N-methyl-carbamate3,5-dimethyl-4-methoxycarbonylamino-phenyl-N- methyl-carbamateZ-y-methylthiopropylphenyl-N-methyl-carbamate3-(a-methoxymethyl2-propenyl)-phenyl-N-methylcarbamate2-chloro-5-tert.-butyl-phenyl-N methyl-carbamatc4-(methyl-propargylamino)-3,S-xylyl-N-methylcarbamate4-(methyl-y-chloroallylamino)-3,5-xylyl-N-methylcarbamate4-(methyl'B-chloroallylamino)-3,5-xylyl-N-methylcarbamatel-(,8-ethoxycarbonylethyl)-3-methyl-5-pyrazolyl-N,N- dimethylcarbamate3-methyl-4-(dimethylamino-methylmercaptomethyleneimino)-phenyl-N-methyl-carbamate1,3-bis(carbamoylthio )-2-( N,N-dimethylamino)- propanehydrochloride5,5-dimethylhydroresorcinoldimethylcarbamateZ-[ethyl-propargylamino]-phenyl-N-methylcarbamate2-[methyl-propargylamino]-phenyl-N methylcarbamate4-[dipropargylamino]-3-tolyl-N-methylcarbamate4-[dipropargylamino]-3,5-xylyl-N-methylcarbamate2-[allyl-isopropylaminol-phenyl-N-methylcarbamate3-[allyl-isopropylaminol-phenyl-N-methylcarbamate ChlorinatedHydrocarbons y-hexachlorocyclohexane [GAMMEXANE; LlNDAN; y HCH]l,2,4,5,6,7,8,8-octachloro-3a,4,7,7a-tetrahydro-4,7- methylene indane[CHLORDAN] l,4,5,6,7,8 ,8-heptachloro-3a,4,7,7a-tetrahydro-4,7-methylene indane [HEPTACHLOR] l ,2,3,4,10, l O-hexachloro-l,4,4a,5,8,8a-hexahydroendo-l,4-exo-5,8-dimethanonaphthalene [ALDRIN]l,2,3,4,l0,lO-hexachloro-6,7-epoxy-l,4,4a,5,6,7,8,8aoctahydro-exo-l,4-endo-5 ,8-dimethanonaphthalene [DIFLORIN]l,2,3,4,l0,lO-hexachlorodJ-epoxy-l,4,4a,5,6,7,8,8aoctahydro-endo-endo-5,8-dimethanonaphthalene[EN- DRIN] The compounds of the formula l may be used as pure activesubstance or together with suitable carriers and- /or additives.Suitable carriers and additives can be solid or liquid and correspond tothe substances conventionally used in formulation technique such, forexample, as solvents, dispersants, wetting agents, adhesives,thickeners, binders and/or fertilisers.

For application, the compounds of the formula 1 may be processed todusts, emulsion concentrates, granules, dispersions, sprays, tosolutions, or suspensions, in the conventional formulation which iscommonly employed in application technology. Mention may also be made ofcattle dips and spray races, in which aqueous preparations are used.

The agents according to the invention are manufactured in known mannerby intimately mixing and/or grinding active substances of the formula Iwith the suitable carriers, optionally with the addition of dispersantsor solvents which are inert towards the active substances. The activesubstances may take, and be used in, the following forms:

Solid forms:

Dusts, tracking agents, granules, coated granules, im-

a. active substances which aredispersible in water;

wettable powders, pasts, emulsions;

b, solutions.

To manufacture solid forms (dusts, tracking agents), the activesubstances are mixed with solid carriers. Suitable carriers are, forexample: kaolin, talcum. bolus, loess, chalk, limestone, groundlimestone. attacluy. dolomite, diatomaceous earth, precipitated silica,alkaline earth silicates, sodium and potassium aluminum silicates(feldspar and mica), calcium and magnesium sulphates, magnesium oxide,ground synthetic materials, fertilisers, for example ammonium sulphate,ammonium phsophate, ammonium nitrate, urea, ground vegetable products,such as corn meal, bark dust, sawdust, nutshell meal, cellulose powder,residues of plant extractions, activated charcoal etc. These substancescan either be used singly or in admixture with one another.

Granules can be very easily manufactured by dissolving an activesubstance of the formula I in an organic solvent and applying theresulting solution to a granulated material, for example attapulgite,SlO

granicalcium, bentonite etc, and then evaporating the sq v at Polymergranules can also be manufactured by mixing the active substances of theformula I with polymerisable compounds (urea/formaldehyde;dicyandiamide/formaldehyde; melamine/formaldehyde or others), whereupona mild polymerisation is carried out that does not affect the activesubstances and in the process of which the granulation is carried outduring the gel formation. It is more advantageous to impregnatefinished, porous polymer granules (urea/formaldehyde, polyacrylontrile,polyester or others) which have a specific surface area and a favourablepredeterminable adsorption/desorption ratio, with the active substances,for example in the form of their solutions (in a low boiling solvent)and to remove the solvent. Polymer granules of this kind in the form ofmicrogranules having a bulk density of 300 g/liter to 600 g/liter canalso be manufactured with the aid of atomisers. The dusting can becarried out from aircraft over extensive areas of cultures of usefulplants.

It is also possible to obtain granules by compacting the carrier withthe active substance and carriers and To these mixtures can also beadded additives which stabilise the active substance and/or non-ionic,anionic and cationic surface active substances, which, for example,improve the adhesion of the active ingredients on plants or parts ofplants (adhesives and agglutinants) and/or ensure a better wettability(wetting agents) and dispersibility (dispersing agents). Examples ofsuitable adhesives are the following: olcin/chalk mixture, cellulosederivatives (methyl cellulose, carboxymethyl cellulose), hydroxyethylglycol ethers of monoalkyl and dialkyl phenols having 5 to 15 ethyleneoxide radicals per molecule and 8 to 9 carbon atoms in the alkylradical, lignin sulphonic acids, their alkali metal and alkaline earthmetal salts, polyethylene gylcol ethers (carbowaxes), fatty alcoholpolyethylene glycol ethers having 5 to 20 ethylene oxide radicals permolecule and 8 to 18 carbon atoms in the fatty alcohol moiety,condensation products of ethylene oxide/propylene oxide, polyvinylpyrrolidones, polyvinyl alco hols, condensation products of urea andformaldehyde.

al als lateis prq ists The water-dispersible concentrates of the activesubstance, i.e. wettable powders, pastes and emulsifiable concentrates,are agents which can be diluted with water to any concentration desired.They consist of active substance, carrier, optionally additives whichstabilise the active substance, surface-active substance and anti-foamagents and, optionally, solvents.

wettable powders and pastes are obtained by mixing and grinding theactive substances with dispersing agents and pulverulent carriers insuitable apparatus until homogeneity is attained. Suitable carriers are,for example, those mentioned for the solid forms of application. In somecases it is advantageous to use mixtures of different carriers. Asdispersing agents there can be used, for example, condensation productsof sulphonated naphthalene and sulphonated naphthalene derivatives withformaldehyde, condensation products of naphthalene or naphthalenesulphonic acids with phenol and formaldehyde, as well as alkali,ammonium and alkaline earth metal salts of lignin sulphonic acid, inaddition, alkylaryl sulphonates, alkali and alkaline earth metal saltsof dibutyl naphthalene sulphonic acid, fatty alcohol sulphates such assalts of sulphated hexadecanols, heptadecanols, octadecanols, and saltsof sulphated fatty alcohol glycol ethers, the sodium salt of oleoylethionate, the sodium salts of oleoyl methyl tauride, ditertiaryacetylene glycols, dialkyl dilauryl ammonium chloride and fatty acidalkali and alkaline earth metal salts.

Suitable anti-foam agents are silicones.

The active substances are mixed, ground, sieved and strained with theadditives cited hereinabove, in such a manner that, the size of thesolid particles does not exceed 0.02 to 0.04 pt in wettable powders, and0.03 p. in pastes. To produce emulsifiable concentrates and pastes,dispersing agents such as those cited above, organic solvents, and waterare used. Examples of suitable solvents are: alcohols, benzene, xylene,toluene, dimethyl sulphoxide, and mineral oil fractions which boilbetween 120 and 350C. The solvents must be practically odourless, notphytotoxic, and inert to the active substances.

Furthermore, the agents according to the invention can be applied in theform of solutions. For this purpose the active substances, or severalactive substances of the general formula 1, are dissolved in suitableorganic solvents, mixtures of solvents or in water. Aliphatic andaromatic hydrocarbons, chlorinatedderivatives thereof, alkylnaphthalenes, and mineral oils, sin gly or in admixture with each other,can be used as organic solvents.

The content of active substance in the above described agents is between0.1% to 95%, in which connection it should be mentioned that, in thecase of application from aircraft or some other suitable means ofapplication, it is possible to use concentrations of up to 99.5% or evenpure active substance.

The active substances of the formula I can, for example, be formulatedas follows: Dusts The following substances are used to manufacture (a) aand (b) a 2% dust:

a. 5 parts of active substance 95 parts of talcum b. 2 parts of activesubstance 1 part of highly disperse silicic acid 97 parts of talcum.

The active substances are mixed with the carriers and ground.

Granules The following substances are used to produce 59; granules:

5 parts of active substance,

0.25 parts of epichlorohydrin,

0.25 parts of cetyl polyglycol ether,

3.50 parts of polyethylene glycol,

91 parts of kaolin (particle size 0.3 0.8 mm).

The active substance is mixed with epichlorohydrin and dissolved with 6parts of acetone; the polyethylene glycol and cetyl polyglycol ether arethen added. The thus obtained solution is sprayed on kaolin, and theacetone subsequently evaporated in vacuo. fittable powder The followingconstituents are used for the preparation of (a) a 40%, (b) and (c) a25%, and (d) a 10% wettable powder:

a. 40 parts of active substance,

5 parts of sodium lignin sulphonate,

1 part of sodium dibutyl-naphthalene sulphonate,

54 parts of silicic acid.

b. 25 parts of active substance,

4.5 parts of calcium lignin sulphonate,

1.9 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1),

1.5 parts of sodium dibutyl naphthalene sulphonate,

19.5 parts of silicic acid,

19.5 parts of Champagne chalk,

28.1 parts of kaolin.

c. 25 parts of active substance,

2.5 parts of isooctylphenoxy-polyoxyethylene ethanol,

1.7 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1),

83 parts of sodium aluminum silicate,

16.5 parts of kieselguhr,

46 parts of kaolin.

d. 10 parts of active substance,

3 parts ofa mixture of the sodium salts of saturated fatty alcoholsulphates,

5 parts of naphthalenesulphonic acid/formaldehyde condensate,

The active substances are intimately mixed, in suitable mixers, with theadditives, the mixture being then ground in the appropriate mills androllers. wettable powders are obtained which can be diluted with waterto give suspensions of any desired concentration. Emulsifiableconcentrates The following substances are used to produce (a) a 10% and(b) a 25% emulsifiable concentrate:

a. 10 parts of active substance,

3.4 parts of epoxidised vegetable oil,

13.4 parts ofa combination emulsifier consisting of fatty alcoholpolyglycol ether and alkylarylsulphonate calcium salt,

40 parts of dimethylformamide,

43.2 parts of xylene.

b. 25 parts of active substance,

2.5 parts of epoxidised vegetable oil,

10 parts of an alkylarylsulphonate/fatty alcoholpolyglycol ethermixture,

5 parts of dimethylformamide.

57.5 parts of xylene.

From these concentrates it is possible to produce, by dilution withwater, emulsions of any desired concentration.

13 Spray The following constituents are used to prepare a 5% spray:

5 parts of active substance, 1 part of epichlorohydrin,

94 parts of benzine (boiling limits 160 190C),

36 g of potassium O-ethyl-S-propyldithiophosphate and 2 g of potassiumiodide are given to 150 ml of acetonitrile. Then 41 g of bromosuccinicacid bismethoxyethyl ester are added and the mixture is stirredovernight at room temperature and subsequently for 6 hours at 50C60c.After the batch has cooled. the salts are filtered off with suction, thesolution is evaporated in vacuo, and the residue is taken up inmethylene chloride. The solution is washed successively with 50 ml ofwater, 50 ml of normal sodium hydroxide solution, and 50 ml of water,and the solvent is removed in c H O O vacuo at 50C bath temperature, toleave as residue the 2 5 active substance of the above described formulaas a 1 S-CH-COOCII Ori -OCH yellow oil with the refractive index n1.5681. Yield: (n) O H S CH COOCH 15 50.1 g. The following compounds arealso obtained in 5 7 2 2 2 5 analogous manner.

Compound Physical Data 0 J 0 161 ll 24 Ps cfi-coi -i(cu -cir=cH n 1 fn)CH S l 2 2 2 D CH -C ON CH -CH=CH O C H ll 2 2 5 1 s-cHC0oc H oo H 00 B144618 (n)c H s l 4 5 CH --COOC 11 00 11 00 11 P-SCHCOOCH (n)@ H s 2 28.15523 ca co0cu 0 13 11 IP-S-CH-COOC H OCH n C H S 5 '7 115 1,5681 OH-COOC H OCH 24 2 P-scs-cou(cii 105126 (n)C H S l 3 (iI-I COlHCH 2 A.Insecticidal ingest poison action Tobacco and potato plants were sprayedwith a' 0.05% aqueous active substance emulsion (obtained from a 10%emulsifiable concentrate.

After the coating had dried. the tobacco plants were populated withSpodoptera littoralis caterpillers in the L stage and Heliothisvirescens caterpillers in the L stage and the potato plants withColorado bettle larvae (Leprinorarra decemlineata). The test was carriedout at 24C and 60% relative humidity. In the above test, the

compounds according to Example 1 displayed good infabac.

EXAMPLE 3 Action against C/zi/u suppressalis Six rice plants at a timeof the variety Caloro were transplanted in plastic pots (diameter at the.top 17 cm) and reared to a height of about 60 cm. Infestation withChilo suppressalis larvae (L; 3-4 mm in length) took place 2 days afterthe active substance had been applied in granule form to the paddy water(rate of application: 8 kg of active substance per hectare). Evaluationof the insecticidal action ensued 10 days after application of thegranules.

In the above test, the compounds according to Example I acted againstChi/ suppressalis.

EXAMPLE 4 Action against ticks A. Rhipicephalus bursa Five adult ticksor 50 tick larvae were counted into a test tube and immersed for I to 2minutes in 2 ml of an aqueous emulsion series each containing I00, l and0.1 ppm of test substance. The tube was then sealed with a standardisedcotton wool plug and stood on its head so as to enable the cotton woolto absorb the active substance emulsion.

In the case of the adults evaluation took place after 2 weeks, and inthat of the larvae after 2 days. Each test was repeated twice.

B. Boophilus nzicroplus (larvae) Tests were carried out with sensitiveand 20 OP resistant larvae with a dilution series analogous to that usedin Test A. (The resistance refers to the tolerability of diazinon). Inthese tests, the compounds according to Example I acted against adultsand larvae of Rhipicephalus bursa and sensitive and OP-resistant larvaeof Boophilus microplus.

EXAMPLE 5 Action against spider mites Phaseolus vulgaris (plants) wereoverlaid with an infested piece of leaf from a mass culture ofTetranyc'hus urricae 12 hours before the test for acaricidal action. Themobile stages which had spread over the plants were sprayed with theemulsified test preparations from a chromatography atomiser so that thespray broth did not run off. The number of living and dead larvae,adults and eggs were evaluated after 2 to 7 days under a stereoscopicmicroscope and the result was expressed in percentages. During the*interim". the treated plants were kept in greenhouse compartments at25C.

In the above test. the compounds according to Example I acted againstadults larvae and eggs of Tammyc/zur urll'cae.

I claim:

l. Thiol phosphoric acid esters of the formula wherein R representsmethyl or ethyl. R represents n-propyl, n-butyl, i-butyl, sec.butyl.n-pentyl. sec.pentyl, or methoxyethyl, R and R each representsmethoxyethoxy, ethoxyethoxy, ethoxyethoxyethoxy. benzyloxy, or the groupin which R and R each represents hydrogen, methyl. or allyl.

2. Compounds according to claim I, wherein R represents n-propyl,n-amyl, sec.amyl or methoxyethyl.

3. Compounds according to claim 1, wherein R and R represent benzyloxyor methoxyethoxy.

4. Compounds according to claim 1 wherein R represents n-propyl,n-pentyl, sec.pentyl or methoxyethyl. and R and R represent benzyloxy ormethoxyethoxy.

5. O-ethyI-S-n-propyl-S-[ l .2-bis(benzyloxycarbonyl)-ethyl]-dithiophosphate according to claim 4.

6. O-ethyl-S-n-propyl-S-[ 1.2-bis-(methoxyethoxycarbonyl)-ethyl]-dithiophosphate according to claim 4.

7. O-ethyl-S-n-propyl-S-[1.2-bis(diallylaminocarbonyl)-ethyl]-dithiophosphate according to claim 2.

1. THIOL PHOSPHORIC ACID ESTERS OF THE FORMULA
 2. Compounds according toclaim 1, wherein R2 represents n-propyl, n-amyl, sec.amyl ormethoxyethyl.
 3. Compounds according to claim 1, wherein R3 and R4represent benzyloxy or methoxyethoxy.
 4. Compounds according to claim 1wherein R2 represents n-propyl, n-pentyl, sec.pentyl or methoxyethyl,and R3 and R4 represent benzyloxy or methoxyethoxy. 5.O-ethyl-S-n-propyl-S-(1,2-bis-(benzyloxycarbonyl)-ethyl)-dithiophosphateaccording to claim
 4. 6.O-ethyl-S-n-propyl-S-(1,2-bis-(methoxyethoxycarbonyl)-ethyl)-dithiophosphateaccording to claim
 4. 7.O-ethyl-S-n-propyl-S-(1,2-bis(diallylaminocarbonyl)-ethyl)-dithiophosphateaccording to claim 2.